Abstract: Medium- and low-temperature coal tar is an important byproduct of the coal pyrolysis process. It contains a high concentration of phenolic compounds and represents a valuable non-petroleum-based phenolic resource. However, due to its complex composition, wide boiling range, significant overlap with hydrocarbon components, and the close boiling points of some isomers, separation and recovery are challenging, which limits its high-value utilization. This paper provides a systematic review of separation technologies and application pathways for phenolic compounds in medium- and low-temperature coal tar, with a focus on the mechanisms of action, applicable targets, technical characteristics, and application potential of green extraction, adsorption separation, and coupled enhancement processes. Based on this, their utilization methods are categorized into two types: the directed conversion of high-purity phenolic monomers and the direct utilization of mixed phenols and phenolic oil fractions. The former is primarily used for the preparation of pesticides, pharmaceutical intermediates, high-performance polymers, and molecular light-storage and heat-storage materials, while the latter is suitable for large-scale applications with relatively lower purity requirements, such as road asphalt modification and functional carbon materials. In the future, efforts should balance separation efficiency, process energy consumption, and product value-added potential, while strengthening hierarchical separation and cascading utilization. Additionally, attention should be focused on the direct high-value conversion of mixed phenols and phenolic oil fractions for use in energy storage functional materials.